US4504675A - Method for making isobutyric acid or esters thereof - Google Patents

Method for making isobutyric acid or esters thereof Download PDF

Info

Publication number
US4504675A
US4504675A US06/436,467 US43646782A US4504675A US 4504675 A US4504675 A US 4504675A US 43646782 A US43646782 A US 43646782A US 4504675 A US4504675 A US 4504675A
Authority
US
United States
Prior art keywords
gas
organic compounds
water
alkanol
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/436,467
Other languages
English (en)
Inventor
Siegmund Besecke
Hermann-Josef Siegert
Gunter Schroder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Assigned to ROHM GMBH, DARMSTADT, reassignment ROHM GMBH, DARMSTADT, ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BESECKE, SIEGMUND, SCHROEDER, GUENTER, SIEGERT, HERMANN-JOSEF
Application granted granted Critical
Publication of US4504675A publication Critical patent/US4504675A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the present invention relates to an improved method for the continuous preparation of isobutyric acid or an ester thereof by the Koch synthesis from propylene, carbon monoxide, and water or an alcohol, preferably a lower alkanol, in the presence of hydrogen fluoride as a catalyst. More in particular the invention relates to an improved method which can be practised on an industrial scale.
  • the present invention particularly concerns the problem of purging the gaseous component of the reaction mixture of secondary constituents present therein.
  • the gaseous starting materials of the Koch synthesis, propylene and carbon monoxide always contain small amounts of impurities such as carbon dioxide, hydrogen, methane and other saturated hydrocarbons, nitrogen, etc. Moreover, gaseous byproducts such as isopropyl fluoride may be formed during the reaction, and these will not react further, or then only partially. Since the isobutyric acid or isobutyric ester reaction product is formed in the liquid phase of the reaction mixture and is recovered from that phase, the gaseous phase of the reaction mixture in principle need not be replaced if the portions consumed during the reaction are continuously replenished. If they are, the concentration of said secondary constituents gradually increases.
  • the practice is to eliminate such constituents after they have reached a certain concentration by the continuous withdrawal of a portion of the gaseous phase in which the amount of the secondary constituents corresponds to that present in the continuous feed and that newly formed.
  • the portion of the gas phase withdrawn contains substantial amounts of hydrogen fluoride which must not be allowed to get into the atmosphere. It must therefore be extracted from the off gas, for example with milk of lime.
  • this is an unsatisfactory solution because of the loss of hydrogen fluoride.
  • the object of the present invention is to improve the Koch synthesis of isobutyric acid or its alkyl esters by the elimination of secondary constituents of the gaseous component of the reaction mixture so that no hydrogen fluoride and no organic fluorine compounds such as isopropyl fluoride or isobutyric acid fluoride get into the atmosphere, or are lost as unusable reaction products, or must be worked up at an expenditure of energy or materials.
  • This object is accomplished by adding oxygen to the gas withdrawn from the reaction space or from a processing arrangement and at least partially burning the organic compounds carried by said gas, whereby the organic fluorine compounds form hydrogen fluoride, and then contacting the gases of combustion in an absorber with water or an alkanol and conducting the liquid containing the hydrogen fluoride to the reaction space. Since the reaction requires water or a lower alkanol anyway, the use of water or an alkanol in the recovery of hydrogen fluoride from the withdrawn portion of the gas does not involve an additional expenditure of materials.
  • the hydrogen fluoride is scrubbed from the off gas stream to such an extent that the residual amounts remaining in the off gas are negligible and, if necessary, can be retained on a basic absorbent such as bauxite, lime, or milk of lime in an absorption column disposed downstream.
  • a basic absorbent such as bauxite, lime, or milk of lime in an absorption column disposed downstream.
  • the water or alkanol with the absorbed hydrogen fluoride can be fed directly into the reaction mixture without requiring prior fractionation, concentration, or other conditioning. Loading of the off gas or waste water from the manufacturing plant with hydrogen fluoride thus is positively prevented.
  • the conventional Koch synthesis is carried out in two steps.
  • an olefin is reacted with carbon monoxide in the presence of a Koch catalyst.
  • the intermediate product formed is reacted further in a second step with water or an alkanol to give carboxylic acid or esters thereof.
  • the two process steps are carried out in separate reaction spaces.
  • water or an alkanol is added to the reaction mixture at the outset so that carboxylic acid or esters thereof are formed immediately.
  • the invention can be used with both variants of the process by feeding the water or alkanol carrying hydrogen fluoride to the appropriate reaction space.
  • the invention is used to great advantage in the preparation of free isobutyric acid, the water used in the reaction serving as absorbent.
  • FIG. 2 is a flow diagram illustrating such treatment of the off-gas in more detail and schematically illustrating suitable apparatus therefor.
  • isobutyric acid or its esters For the preparation of isobutyric acid or its esters according to the invention, at least 1 mole of water or 1 mole of an alkanol and from 5 to 20 moles of hydrogen fluoride are used per mole of propylene used.
  • the preferred alkanol is methanol.
  • Other suitable alkanols are ethanol, propanol, isopropanol, and n-butanol or isobutanol.
  • the total amount of water or alkanol used in the reaction is preferably used as scrubbing liquid in the absorber; however, this amount need not be greater than 2 moles per mole of propylene used.
  • the release from pressure causes previously dissolved gaseous constituents, and particularly hydrogen fluoride, to be liberated.
  • gaseous contaminants to be purged When a substantial amount of the gaseous contaminants to be purged is so released, it is sufficient to conduct only the gases so evolved in flashing through the absorber. There will then be no need to withdraw gas directly from the pressurized zone.
  • the pressure may be reduced in several stages, for example, first to from 2 to 10 bars, then to atmospheric pressure, with gases evolving each time. In general, it is not economical to compress this corrosive gas in order to be able to return it to the reaction chamber. For this reason it is usually piped to the absorber and, after combustion of the organic constituents and removal of the hydrogen fluoride by scrubbing, discharged to the atmosphere.
  • the stream of gas evolved upon the flashing of the liquid phase is not sufficient for the purging of the gaseous contaminants formed, a portion of the gas phase must be withdrawn from the pressurized zone.
  • the gas phase is not scrubbed under pressure, it is expanded and preferably combined with the gas evolving from the liquid phase.
  • water or alkanol carrying hydrogen fluoride is obtained which is piped to the pressurized zone by means of a suitable pump for liquids.
  • the gas should be preheated, preferably to 300° to 700° C. This may be done by indirect heating through a heat exchanger.
  • the gases of combustion leaving the catalyst bed, or other gases burning with a flame, may then be used as heating media.
  • the gas to be burned may be mixed directly with another hot gas and the gas mixture formed may then be conducted over the catalyst.
  • first absorber stage 12 may be operated under pressure.
  • an expansion valve (not shown) is disposed in the passage to combustion chamber 13 and the scrubbing liquid is piped from antechamber 15 to the top of the absorber 12 by means of a pressure pump (cf. FIG. 1).
  • absorbers 12 and 16 contain conventional packing. Like all other parts of the absorption unit, this packing is fabricated from a material that is resistant to hydrogen fluoride or hydrofluoric acid, respectively. Suitable materials include aluminum, nickel-chromium-iron alloys, and polytetrafluroethylene or similar fluorinated polymers.
  • the amount of gas withdrawn should be large enough for the fraction of gaseous contaminants and undesired gaseous byproducts which it carriers to correspond to that present in the continuous feed and newly formed. Since some of the propylene and carbon monoxide is always lost with the gaseous contaminants, the partial pressure of the latter is advantageously held high. For this reason, the partial pressure of the gaseous contaminants in the gas phase in the reactor should be allowed to rise to a level that falls just short of having an adverse effect on the progress of the reaction. Under steady state operating conditions, the partial pressure of the gaseous contaminants will be constant. That partial pressure should not exceed 30 bars, if possible. The total pressure should be held so high that, after subtraction of the partial pressure of the gaseous contaminants, the pressure of the reacting gases (propylene, carbon monoxide and hydrogen fluoride) is high enough to assure the desired reaction rate.
  • the reacting gases propylene, carbon monoxide and hydrogen fluoride

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
US06/436,467 1981-11-14 1982-10-25 Method for making isobutyric acid or esters thereof Expired - Fee Related US4504675A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3145311 1981-11-14
DE19813145311 DE3145311A1 (de) 1981-11-14 1981-11-14 Verfahren zur herstellung von isobuttersaeure oder ihren alkylestern

Publications (1)

Publication Number Publication Date
US4504675A true US4504675A (en) 1985-03-12

Family

ID=6146427

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/436,467 Expired - Fee Related US4504675A (en) 1981-11-14 1982-10-25 Method for making isobutyric acid or esters thereof

Country Status (4)

Country Link
US (1) US4504675A (fr)
EP (1) EP0079497B1 (fr)
JP (1) JPS5896039A (fr)
DE (2) DE3145311A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749525A (en) * 1986-07-02 1988-06-07 Ashland Oil, Inc. Process for the carbonylation of propylene
US4838998A (en) * 1985-01-09 1989-06-13 Rohm And Haas Company Process for separating sulfuric acid and carboxylic acids
EP0336996A1 (fr) * 1988-04-15 1989-10-18 Elf Atochem S.A. Procédé de carbonylation du propylène
US5169985A (en) * 1989-01-25 1992-12-08 Rohm Gmbh Continuous method for making isobutyric acid
KR100580075B1 (ko) * 2002-12-10 2006-05-16 주식회사 엘지화학 이소부티릭산의 정제방법

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3821155A1 (de) * 1988-06-23 1989-12-28 Roehm Gmbh Verfahren zur abtrennung von fluorwasserstoff aus isobuttersaeure oder ihren alkylestern
DE3902104A1 (de) * 1989-01-25 1990-07-26 Roehm Gmbh Kontinuierliches verfahren zur herstellung von isobuttersaeure
JP5044947B2 (ja) * 2005-03-10 2012-10-10 三菱瓦斯化学株式会社 カルボン酸あるいはカルボン酸エステルの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052698A (en) * 1958-10-27 1962-09-04 Sinclair Research Inc Ester production
US3461157A (en) * 1966-05-27 1969-08-12 Union Oil Co Process for the oxidation of olefins with a platinum group metal catalyst
US4255591A (en) * 1978-11-20 1981-03-10 Monsanto Company Carbonylation process
US4303594A (en) * 1980-04-25 1981-12-01 Ashland Oil, Inc. Process for the production of isobutyric acid anhydride

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1567494B2 (de) * 1962-08-16 1972-02-24 Farbwerke Höchst AG, vormals Meister Lucius & Brüning, 6000 Frankfurt Verfahren zur gewinnung bzw entfernung von fluorwasserstoff ausgasmischungen
FR2330436A1 (fr) * 1975-11-04 1977-06-03 Rhone Poulenc Ind Procede d'absorption de composes fluores presents dans des melanges gazeux
BE888902A (fr) * 1981-05-21 1981-09-16 Steuler Industriewerke Gmbh Procede et dispositif pour separer des melanges d'air et de gaz les impuretes difficilement absorbables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052698A (en) * 1958-10-27 1962-09-04 Sinclair Research Inc Ester production
US3461157A (en) * 1966-05-27 1969-08-12 Union Oil Co Process for the oxidation of olefins with a platinum group metal catalyst
US4255591A (en) * 1978-11-20 1981-03-10 Monsanto Company Carbonylation process
US4303594A (en) * 1980-04-25 1981-12-01 Ashland Oil, Inc. Process for the production of isobutyric acid anhydride

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of Organic Chemistry, vol. 37, No. 12, (1972), pp. 1971 1975, Norell, J. R. *
Journal of Organic Chemistry, vol. 37, No. 12, (1972), pp. 1971-1975, Norell, J. R.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4838998A (en) * 1985-01-09 1989-06-13 Rohm And Haas Company Process for separating sulfuric acid and carboxylic acids
US4749525A (en) * 1986-07-02 1988-06-07 Ashland Oil, Inc. Process for the carbonylation of propylene
EP0336996A1 (fr) * 1988-04-15 1989-10-18 Elf Atochem S.A. Procédé de carbonylation du propylène
US5169985A (en) * 1989-01-25 1992-12-08 Rohm Gmbh Continuous method for making isobutyric acid
KR100580075B1 (ko) * 2002-12-10 2006-05-16 주식회사 엘지화학 이소부티릭산의 정제방법

Also Published As

Publication number Publication date
JPS6313416B2 (fr) 1988-03-25
DE3145311A1 (de) 1983-05-26
EP0079497B1 (fr) 1985-04-10
JPS5896039A (ja) 1983-06-07
EP0079497A1 (fr) 1983-05-25
DE3263021D1 (en) 1985-05-15

Similar Documents

Publication Publication Date Title
SU893126A3 (ru) Способ очистки уксусной кислоты
RU2178411C2 (ru) Способ разделения смеси газообразных продуктов, образующихся в процессе каталитического синтеза метилмеркаптана
EP0003530B1 (fr) Procédé de préparation du phosgène
US6387345B1 (en) Process for working up reaction gases during the oxidation HCI to chlorine
MXPA06008721A (es) Procedimiento para el aislamiento de acetato de vinilo.
EP2089352B1 (fr) Procédé de préparation d'acétate de vinyle
US4504675A (en) Method for making isobutyric acid or esters thereof
CA2085876C (fr) Production d'oxyde d'ethylene
US4094962A (en) Process for producing hydrogen and sulfur from hydrogen sulfide
EP1189863B1 (fr) Systeme de recuperation de l'ethylene
US4046866A (en) Production of liquid sulfur trioxide
US4351819A (en) Recovery of chlorine values in integrated process for oxychlorination and combustion of chlorinated hydrocarbons
US5998489A (en) Methanol preparation process
WO2015193328A1 (fr) Procede et appareil pour le traitement de degagement gazeux dans une unite de production d'acide acetique
US3312719A (en) Process for oxidizing hydrocarbons
CS198231B2 (en) Method of the partial separation of water from gas mixture arising in vinyl acetate preparation
HU188556B (en) Process for production of 1,2-dichlor ethan
US4310713A (en) Production of 1,2-dichloroethane
US4324932A (en) Process for the manufacture of vinyl chloride by the thermal cracking of 1,2-dichloroethane
US5514829A (en) Process for continuously producing dimethyl carbonate
KR20040086368A (ko) 아크롤레인의 정제 방법
US4346069A (en) Recovery of chlorine values in integrated process for oxychlorination and combustion of chlorinated hydrocarbons
US3296314A (en) Process for purifying methyl ether
US4237073A (en) Process for the manufacture of acetaldehyde
US3428423A (en) Method for the removal and recovery of promoter from crude phthalic anhydride made by the vapor phase oxidation of orthoxylene in the presence of promoter

Legal Events

Date Code Title Description
AS Assignment

Owner name: ROHM GMBH, DARMSTADT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BESECKE, SIEGMUND;SIEGERT, HERMANN-JOSEF;SCHROEDER, GUENTER;REEL/FRAME:004275/0484

Effective date: 19821011

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19970312

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362